Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/692—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus
  • C08G63/6924—Polyesters containing atoms other than carbon, hydrogen and oxygen containing phosphorus derived from polycarboxylic acids and polyhydroxy compounds
  • C08G63/6926—Dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
  • C07F9/02—Phosphorus compounds
  • C07F9/28—Phosphorus compounds with one or more P—C bonds
  • C07F9/50—Organo-phosphines
  • C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
  • C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)

Definitions

• the invention relates to phosphorus-containing polyarylene esters, which are of interest as highly temperature-resistant and flame-retardant thermoplastics.
• polyester phosphonates which belong to the same class of plastics in terms of their properties. However, due to the content of phosphonic ester groups, they are relatively easily hydrolytically cleavable.
• Phosphorus-containing polyarylene esters are described in JP-OS 81 65020 and in a work by H. Kondo et al. (- 588 European Polymer Journal, 17 1981, p 583 vol.) Described. They contain the phosphorus atoms in 5- or 6-membered ring structures that strongly stiffen the polymer molecule. This leads to high softening temperatures which require processing close to the decomposition temperature.
• the melting temperature of a co-condensate in which about 30% of groups A are replaced by residues of bisphenol A, is only about 250 ° C. This reduction in the melting temperature, which is desirable but not yet sufficient for processability, must be bought with a reduction in the phosphorus content by 28%.
• the melting temperature of phosphorus-containing polyarylene esters should be reduced further without simultaneously reducing the phosphorus content.
• Amorphous, thermoplastically processable plastics without partially crystalline areas with glass transition temperatures not exceeding 200 ° C are sought. This goal is achieved in that the links B from at least two different or bridged aromatic residues exist.
• the polyarylene esters according to the invention are distinguished from those which each contain only one type of group A and B by a markedly reduced tendency to crystallize. This is due to a disruption of the crystalline structure, which in turn is due to a reduced periodicity of the chain structure.
• the new polyarylene esters can be molded in the thermoplastic state below their thermal decomposition temperature in the temperature range from about 200 to 380 ° C to films, fibers, profiles or other shaped articles which are characterized by good self-extinguishing properties.
• R which is involved in the construction of the polyarylene esters according to the invention consists at least in part of compounds of the structure
• R can be, for example, a methyl, chloromethyl, benzyl or phenyl group. Methyl and phenyl are preferred.
• the aromatic radicals de., Compound can optionally carry further substituents, such as fused aromatic ring systems, methyl groups or halogen atoms, in particular bromine or chlorine.
• the phenolic hydroxyl groups are preferably in the p-position to the phosphorate cm.
• the oxidized form of the compound, for which x 1, is preferred.
• Some of the phosphorus-containing groups A can be replaced by the phosphorus-free groups mentioned for B. This reduces the phosphorus content of the polyarylene ester, but at the same time further reduces the tendency to crystallize.
• the proportion of phosphorus-free groups A is limited in that the phosphorus content is not less than 1% by weight. may be. It is preferably over 2% by weight; as a rule even over 4 and in particular at 5 to 7 wt .-%.
• the proportion of phosphorus-containing groups A is preferably above 50 mol%, in particular above 70 mol% of the total of groups A.
• the Schotten-Baumann reaction between the bisphenols HO-A-OH and the dicarboxylic acid dichlorides ClCO-B-COCl in the presence of an at least equivalent amount of a base in a suitable solvent is particularly useful.
• suitable solvents are aliphatic chlorinated hydrocarbons, such as methylene chloride, chloroform, tetrachlorethylene, tetrachloroethane, or aromatic hydrocarbons, such as toluene.
• bases for example sodium or potassium hydroxide, pyridine and triethylamine can be used be applied.
• the reaction temperature is, for example, between 0 and 150 ° C, preferably 20 to 100 ° C.
• the starting compounds are used in the highest possible purity.
• monofunctional impurities that participate in the reaction but have a chain-breaking effect are said to be absent.
• the molar ratio of the bisphenols to the total of the dicarboxylic acid derivatives must be very close to 1: 1, which is generally known from the chemistry of the polycondensation reactions.
• the molecular weight of the polyarylene esters is preferably not less than 10,000, preferably in the range from 20,000 to 80,000. To achieve these molecular weights, condensation times of 0.1 to 10 hours are required.
• the plastic properties, especially the strength values of the products, can often be further improved by post-condensation for 10 to 90 minutes at 250 to 350 ° C, if necessary in vacuo.
• the resulting linear macromolecules usually contain hydroxyl or carboxyl groups as Ehd groups, which can, if desired, be etherified or esterified subsequently. Targeted small amounts of monofunctional phenols or carboxylic acids can also be added to form end groups.
• the resulting polymer molecules usually remain dissolved during the condensation, while the hydrochloride of the base precipitates and can be filtered off.
• the polymer can e.g. by precipitation with a non-solvent or by evaporation of the solvent.
• Example 3 Analogously to Example 3, 0.05 mol of oxibis (p-phenylene carbonyl chloride) was used instead of the iso / terephthalic acid dichloride mixture.
• the polyester was first precipitated from petroleum spirit, then from methanol / water.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Biochemistry (AREA)
• General Health & Medical Sciences (AREA)
• Molecular Biology (AREA)
• Polyesters Or Polycarbonates (AREA)

Applications Claiming Priority (2)

Publications (3)

Family

ID=6166166

Family Applications (1)

Country Status (4)

Cited By (1)

Families Citing this family (7)

Family Cites Families (9)

• 1982
  • 1982-06-16 DE DE19823222571 patent/DE3222571A1/de not_active Withdrawn
• 1983
  • 1983-05-31 DE DE8383105363T patent/DE3365120D1/de not_active Expired
  • 1983-05-31 US US06/499,526 patent/US4463159A/en not_active Expired - Fee Related
  • 1983-05-31 EP EP83105363A patent/EP0096799B1/fr not_active Expired
  • 1983-06-10 JP JP58102936A patent/JPS596218A/ja active Pending

Also Published As

Similar Documents

Legal Events